DE2925567A1 - POLYAMINE CONTAINING UREA GROUPS AND THE PRODUCTION AND USE THEREOF AS A RETENTION AGENT - Google Patents

Abstract

Non-crosslinking, water-soluble polyamines which can be obtained by reacting (A) basic polyureas which have been prepared by condensation of ureas with polyamines containing at least three amino groups, of which at least one is a tertiary amino group, or with mixtures of these polyamines with aliphatic, araliphatic, cycloaliphatic or heterocyclic polyamines containing two primary or two secondary amino groups or one primary or one secondary amino group, and optionally with omega -aminocarboxylic acids containing at least three carbon atoms, or lactams thereof, (B) polyalkylenepolyamines of the general formula <IMAGE> in which R denotes H or CH3, the indices y are in each case identical or different and denote the number 0 or 1 and x denotes a number from 4 to 2,500, or mixtures of these polyalkylenepolyamines with amines of the same general formula, but in which x denotes a number from 1 to 3, and (C) compounds which are polyfunctional towards amino groups, are used as agents for increasing the retention of fibres, fillers and pigments, for accelerating the drainage in the production of paper and for working up effluents from paper machines by filtration, sedimentation and flotation.

Description

The invention relates to non-crosslinking, water-soluble Polyamines obtained by reacting

A) basic polyureas produced by condensation of ureas with polyamines containing at least three Contain amino groups, at least one of which is a tertiary amino group, or with mixtures of these Polyamines with two primary or two secondary amino groups or one primary or one secondary amino group containing aliphatic, araliphatic or heterocyclic polyamines and optionally made with at least three carbon atoms containing ^ -aminocarboxylic acids or their lactams have been,

B) Polyalkylenepolyamines of the general formula

15 H ₂ N- [CH ₂ -CH- (CH _{2) y-H} -NHj

R.
in RH or CH

y identically or differently the number O

or 1 and
χ means a number from h "to 25oo

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or mixtures of these polyalkylene polyamines with amines the same general formula but in which

χ is a number from 1 to 3, and

C) Compounds which are polyfunctional towards amino groups are obtainable.

The invention also includes a method for Manufacture of these water-soluble polyamines and their use as agents for increasing retention of fibers, fillers and pigments as well to accelerate dewatering during paper production and to recycle water from paper machines by filtration, sedimentation and

15 flotation.

To produce the water-soluble polyamines according to the invention, higher molecular weight basic polyureas, i.e. polyureas, their average molecular weight is greater than 5,000 is used.

The basic polyureas are in particular Consideration:

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a) conversion products of ureas and polyamines, which contain at least three amino groups, at least one of which is a tertiary amino group or Mixtures of these polyamines. Examples include: methyl bis (3-aminopropyl) amine, N- (2-aminoethyl) piperazine, 4,7-dimethyltriethylenetetramine, Methyl bis (2-aminoethyl) amine, ethyl bis (3-aminopropyl) amine, the first two amines mentioned are preferred.

The following are also mentioned as water-soluble polyureas:

b) those products which, in addition to those under a) specified polyamines have two primary or two secondary or one primary and one secondary Amino group-containing aliphatic, cycloaliphatic, araliphatic or heterocyclic Polyamines, such as ethylenediamine, 1,6-diaminohexane, 1,4-diaminocyclohexane, 1,2-diaminopropane, 1,3-bis-aminomethylbenzene or piperazine, whereby the use of the first two

20 th polyamines is preferred.

c) Such reaction products, "in which per mole of urea up to 0.5 moles of polyalkylenepolyamines such as diethylenetriamine, Triethylenetetramine and higher homologues as well as dipropylenetriamine, tripropylenetetramine and higher homologs besides those mentioned under a) and b) are condensed and their secondary amino groups subsequently unsaturated compounds such as acrylic acid, maleic anhydride or acrylamide can be added.

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The condensation reaction is preferably carried out "at a molar ratio of polyamine to urea of Carried out 1: 1, but it can also be carried out with a ratio of 1: 0.7 to I: 1.5. The reaction temperature can be from 12o to 25o C be varied, it is preferably carried out at temperatures between 1 ^ o and 19o C.

As polyalkylenepolyamines B of the formula H ₃ N- (CH ₂ ) _y -NH [ _x -H, in which R = H or CH ₃ , y is the same

₁₀ or different the number O or 1 and χ = 1

to 3 or h to 2,500 are especially the polyethylene polyamines in which y is zero, for example ethylene diamine, 1,2-propylene diamine, diethylene triamine, dipropylene triamine, triethylene tetramine, tripylene tetramine, tetraethylene pentamine, tetrapropylene pentamine, pentaethylene hexamine, pentapropylene hexamine, hexaeptaethylene haptamine, hexaeptaethylene haptamine, , Heptapropylenoctamine and their mixtures and polyethylene polyamines, which also contain one or more piperazine rings, such as aminoethylpiperazine, pentaethylene pentamine, octaethylene heptamine and mixtures thereof, but in particular

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a) the discontinuous, (e.g. Houben-Weyl, 4th edition, XI / 1, page 44), or in the case of the continuous (e.g. in GB-PS 1,832,534 and 2,049,467) reaction of 1 mole of 1,2-dichloroethane with aqueous Ammonia (6-30 mol), if appropriate in the presence of added ethylenedamine or diethylenetriamine (US Pat. No. 2,769,841 and US Pat. No. 3,484,488) obtained polyethylene polyamine mixture which contains substantial proportions on tetraethylene pentamine, pentaethylene hexamine, hexaethylene hexamine, Contains hexaethyleneheptamine, heptaethyleneheptamine and higher amines, and most importantly

b) after distilling off ethylenediamine, possibly also diethylenetriamine and triethylenetetramine from the base mixture prepared according to a)

15 "permanent polyethylene polyamine blend.

c) by condensation of 1,2-dichloroethane with the often mentioned polyethylene polyamines, individually or in a mixture, polyvalent oligomers which can be prepared Amines with an average molecular weight of 1,000 to 10,000, in particular 2,000 to 5,000,

d) by polymerization of 1,2-alkylenimines obtainable polyvalent amines with an average molecular weight of 1,000 to 10,000, in particular 2,000 to 5,000.

Other polyalkylenepolyamines of the above formula that may be mentioned are:

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e) Pure polypropylene polyamines and their mixtures and

f) mixed polyethylene polypropylene polyamines and mixtures thereof, especially those produced by one or more reactions of ethylenediamine or propylenediamine-1.3 with acrylonitrile and subsequent hydrogenation, e.g. polyvalent amines the formula

I _x -H where χ is an integer from 1 to Io

as well as those of the formula
HJNH-CH ₂ -CH ₂ -Ch ₂ I _m -NH-CH ₂ -CH ₂ -NH-

where m is an integer from 1 to 5 and η is an integer from 0 to 5, moreover

g) by condensation of 1,2-dichloroethane with the polyalkylenepolyamines mentioned under e) and f) polyvalent amines with a average molecular weight of 1,000 to 10,000, in particular 2,000 to 5,000.

2Q In some cases it is advantageous if a part the used polyalkylenepolyamines B by different types of di-, tri-, tetra-, penta- or Hexamines are replaced, e.g. by amines of the formula

Y - [(CH ₂ -CH-CH ₂ -NH) _p -H].

25 in the

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Υ for oxygen, sulfur or the remainder of an at least divalent aliphatic, cycloaliphatic, araliphatic or aromatic hydroxyl and / or sulfhydryl groups 5 connection is established,

R _{3 is} hydrogen or the methyl group,

ρ is an integer of at least 1, preferably 1-3, and

q is an integer of at least 2, preferably 10 2-4.

Representatives of these polyamines are, for example, bis (3-aminopropyl) ether, bis (3-aminopropyl) sulfide, Ethylene glycol bis (3-aminopropyl ether), dithioethylene glycol bxs- (3-aminopropyl ether), Neopentylene glycol bis (3-aminopropyl ether), hexahydro-p-xylylene glycol bis (3-aminopropyl ether) and hydroquinone bis (3-aminopropyl ether),

as well as amines of the formula

^R 5
(CH ₂ -CH-CH ₂ -NH) _r -H

H - ¹

(CH ₂ -CH-CH ₂ -NH) ₃ -H,

in the H ^E 5 uR ₆

^{for a c} i ~ ^c ig- alkyl radical optionally substituted by an amino or hydroxyl group and

independently represent hydrogen or a methyl group and

r and s is a number from 1 to 2o, preferably from 2 to 5.

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Representatives of these polyamines are, for example, ethylbis (3-aminopropyl) amine, 2-hydroxyethyl bis (3-aminopropyl) amine, n-butyl bis (3-aminopropyl) amine, Tris (3-aminopropyl) amine and especially methyl bis (3-aminopropyl) amine.

In the preparation of the water-soluble polyamines according to the invention, the proportions between the basic polyureas A and the polyalkylene polyamines B can vary within wide limits. I ^m are generally preferred such reaction products, the production of which the polyethylene polyamines and the polyureas in Gewiehtsverhältnis of 1 his Io: Io "to 1, especially from 1 to 2.5: 2.5 to 1, preferably from 1 to 1.8: 1.8 to 1

15 can be used.

As compounds which are polyfunctional towards amino groups C, polyfunctional ones, in particular, are suitable for the preparation of the polyamines according to the invention Compounds that in aqueous solution at pH values above 6, preferably above 8, with the in the basic polyamides containing amino groups are able to react completely.

As compounds which are ροIyfunctional towards amino groups are for example:

bifunctional compounds, such as <*, CO-alkyl dihalides, e.g. in particular 1.2-dichloroethane, 1.2-dibromoethane, 1.2-dichloropropane, 1.3-dichloropropane, le-dichlorohexanjO ^ w ¹ -dihaloether, e.g. 2,2'-dichloro-diethylether, bis- (ß-chloro-isopropyl) -ether,

30 bis - (* t -chloro-butyl ether); Halohydrins or

Epihalohydrins, e.g. epichlorohydrin, 1,3-dichloropropanol- (2), Bis (3-chloro-2-hydroxypropyl) ether /

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1,4-dicii-lor-2.5-epoxy-butan;

Bis-epoxy compounds, e.g., 1,2,3,4-diepoxybutane, diglycidyl ether, ethane-1,2-bis-glyeidyl ether;

U-haloarboxylic acid halides, e.g. chloroacetyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride, 3-bromo-propionyl bromide; Vinyl compounds, e.g. divinyl ether, divinyl sulfone, Methylenebisacrylamide;

also 4-Chlonaetliyl-1,3-dioxalanon- (2) and

2-chloroethyl chloroformic acid ester, also chloroformic acid ester, 3-chloro-2-hydroxypropyl ether and glycidyl ether of polyalkylene oxides, e.g. polyethylene oxides, as well as conversion products of

15 1-5o moles of alkylene oxides, such as ethylene oxide and / or Propylene oxide, with 1 mole of di- or polyhydric polyols or other at least two active hydrogen compound containing atoms;

trifunctional compounds such as 1,3,5 -triacryloylhexahydro-s-triazine, and bifunctional alkylating agents of the formula

[Cl- (CH ₂ -CH-CH ₂ - N) _X is -CH ₂ -CH-CH ₂ Cl CI OH R OH ^L:

manufactured

according to ÜS-PS 3 632 559, example 2, 1.

25 Particularly preferred compounds C are dichloroethane and epichlorohydrin.

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The proportions of the polyfunctional compounds to the two components A and B are expedient dimensioned so that the formation of the desired degree of condensation of the water-soluble polyamine is not are significantly exceeded. The minimum amount of compounds C polyfunctional towards amino groups, which are to be used to produce reaction products with the desired high molecular weight or solutions thereof according to the desired viscosity (i.e. 100-1500 mPas, preferably 200-400 mPas of a 25% aqueous solution) obtained are mainly dependent on the molecular weight of the two components and can be determined by preliminary tests Easily determined on a case-by-case basis.

It is important that all functional groups of the compounds C have reacted so that the reaction product is practically free of self-crosslinking groups.

The preparation of the polyamines according to the invention from the basic polyureas A and the polyalkylene polyamines B can be prepared by processes known per se take place, for example, by mixing mixtures of A, B and those polyfunctional with respect to amino groups Compounds C in aq. Media at pH values above 6 and at temperatures between 0 and 140 ° C as long stirs until a sample of the reaction mixture in the form of a lo% aqueous solution has a viscosity at 25.degree of at least Io cP. It is often an advantage to use the mixture of A and B in the water Milieu the polyfunctional compounds under otherwise identical reaction conditions in portions gradually added until the desired viscosity is reached. The content of the reaction solution

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of action products, which is preferably between Io and 3o percent by weight, is then, if the reaction! was carried out at a higher concentration by diluting with water on the desired end value is set. In some cases it is used to cease exposure after reaching the desired viscosity necessary to adjust the pH of the reaction solution by adding acids, e.g. Hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid

10 acid, to be adjusted to pH 6, preferably from h to 5. This is especially true in the event that the minimum amount of functional compounds required for the formation of the desired degree of condensation of the water-soluble polyamine is considerably exceeded

■ J5 has been.

The condensation can also take place in a closed vessel at temperatures above the boiling point of the Compound C polyfunctional towards amino groups, especially when using dihaloalkanes,

2o preferably between 90-130 ° C at pressures of 0-50 bar, preferably 3-8 bar, are carried out. It is not normally necessary to stop the reaction by adding acid.
The total concentration of the components in the aqueous

Reaction mixture should be 10 to 50 percent by weight.

In the preparation of the reaction products according to the invention, the polyfunctional ones need to be converted

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Compound C not necessarily with a mixture from A and B to be done. It is also possible to first use one of the "two components A or B to react with the polyfunctional compound C to form a precondensate and then this to be implemented in the second stage with the other component.

The polyamines according to the invention are by a Minimum molecular weight of 2,500, preferably

10 5 ooo, marked. The upper limit of their molecular weight is due to their property to be soluble in water, given. A numerical description of the upper limit of their molecular weight is not possible as this is heavily dependent on the

■ J5 underlying polyamines and the number of in water-solubilizing groups contained therein depends.

When using the polyamines according to the invention as an aid to increasing the retention of

20 fibers, fillers and pigments as well as dehydration accelerators one proceeds in a manner known per se such that the polyamines according to the invention are in the form of dilute aqueous solutions the paper stock suspension before the cup

adds, the metering point being chosen so that a good distribution of the aid in the raw material suspension is ensured, but too long a contact time is avoided. The amounts of

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Polyamines, which to achieve the desired retention effect and / or dehydrating. accelerating effect are required can be determined by preliminary tests without difficulty; In general, it is advisable to use 0.005 to 0.5 percent by weight of polyamines on the dry weight of the paper to use. The addition of polyamines according to the invention before The headbox of a paper machine is also beneficial in the processing of paper machine waste water by filtration, flotation or sedimentation; the coagulating effect of the Polyamines according to the invention facilitate the separation of paper stock components from the paper

15 machine wastewater is very important.

When the polyamines according to the invention are used as auxiliaries in the processing of paper machine wastewater by filtration, flotation or sedimentation can also be done in a manner known per se Proceed in a manner, preferably in such a way that the reaction products under consideration in the form of dilute aqueous solutions the paper machine wastewater expediently before entering the Stoffanger clogs.

25 The amounts of polyamines that are sufficient

Cause coagulation of the paper raw material constituents contained in paper machine waste water are

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to be measured according to the composition of the wastewater and let through on a case-by-case basis Easily identify preliminary attempts; in general, amounts of from o.oo5 to 2 g of polyamine are required for this purpose Sufficient per m3 of wastewater.

In comparison with similar known compounds (cf. e.g. ÜS-PS 3 966684) in the application range of pH 4.0 - 8.0 an increase in the retention effectiveness as well as the 10 dewatering acceleration.

The polyamines according to the invention are surprisingly especially effective on paper raw material with a high content of wood pulp.

Some polyamines according to the invention and their uses to increase the retention of fibers,

Fillers and pigments as well as for accelerating dewatering in papermaking are described below.

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Manufacturing examples

Production of the polyureas A polyurea 1

A mixture of 435 g of methyl-l) is (3-aminopropyl) amine and 180 g of urea are heated to 190 ° C. for 1 hour while stirring and passing nitrogen over it heated. It is then cooled to 100 ° C. and so much water is added that a 50% aqueous solution is obtained Solution received.

10 This solution has "at 25 ° C a pH value of 12.5, a viscosity of 56o mPas and a base equivalent of 34o.

Polyurea 2

A mixture of 145 g of methyl bis (3-aminopropyl) 15 amine, 129 g of 2-aminoethylpiperazine and 120 g of urea is heated at 140 ° C. for 5 hours while stirring and passing nitrogen over it. M _a n cooled to 12o ° C, and so is too much water, that a 5o strength #

aqueous solution is obtained. This solution has a pH of 12.2 at 25 C and a viscosity of 23oo mPas and a base equivalent of 32o.

Polyurea 3

A mixture of 129 g of 2-aminoethylpiperazine and 6o g of urea were stirred and passed over heated by nitrogen for 3 hours at 180 ° C. Cool down to 120 ° C and add as much Wagser as that a 50 $ aqueous solution is obtained. This solution has a pH of 11.2 at 25 ° C, a Viscosity of 5,000 mPas and a base equivalent of 3o8.

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Polyurea 4
A mixture of 116 g of methyl bis (3-aminopropyl) amine, 15 g of ethylenediamine and 60 g of urea is heated for 8 hours at 130 ° C. while stirring and passing nitrogen over it. It is cooled to 120 ° C. and sufficient water is added to obtain a 50% aqueous solution. This solution has a pH of 12.3 at 25 C, a viscosity of 318 mPas and a base equivalent of 32o.

IO polyurea 5

A mixture of 35 g of methyl bis (3-aminopropyl) amine, 15 g of ethylenediamine, 51 g of diethylenetriamine and 60 g of urea are stirred and passed over of nitrogen to 190 ° C. within 2 hours

15 heated and a further 2 hours at this temperature

touched. You cool down to 14o ° C ah and put as much Add water so that a 50% strength aqueous solution results.

This solution has a pH of 12.3 at 25 ° C., a viscosity of 72o mPas and a base equivalent of 34o. 36 g of acrylic acid and 40 g of 50% potassium hydroxide solution are added to this solution and the mixture is heated at 60 ° C. for 8 hours. The solution then has a viscosity of 800 mPas at 25 ° C-.

Polyurea 6

25 A mixture of 129 g of 2-aminoethylpiperazine,

30 g of ethylenediamine, 51 g of diethylene, triamine and 12o g Urea is heated for 5 hours at 160 ° C. with stirring. Cool to 120 ° C and set as much Add water so that a 50 $ solution results.

49 g of maleic anhydride and 120 g of 50 potassium hydroxide solution are added to this solution. The thus obtained Solution has a viscosity of 8oo mPas at 25 ° C.

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Production or composition; of the polyalkylenepolyamines B

Polyalkylene polyamine 1

From the reaction mixture obtained by the continuous reaction of dichloro-5 ethane, aqueous ammonia and ethylenediamine in a molar ratio of 1:17: ο Λ at 160 ° - 220 ° C and 100 bar, the excess ammonia is first separated off under pressure and then at 130 - 135 ° C with excess 5o% sodium hydroxide solution, the bases formed from their hydro-

chlorides set free. Most of the water and ethylene diamine are distilled while the higher-boiling bases cut off in liquid form. The base mixture thus obtained contains

15 in addition to 15 - 2o % water and 3 - 5% ethylenediamine, about 15 - 2o % diethylenetriamine, 2-3 $ aminoethylpiperazine, about 1 % H ₂ N-CH ₂ -CH ₂ -NH-Ch ₂ -CH ₂ -OH, 15 - 18% triethylenetetramine, 3 - 4 # tetraethylenetetramine, Io - 14 ° / ° tetraethylene pentaine, 6 - Io #

2o pentaethylene hexamine, as well as around Io - 15 % higher polyethylene polyamines and small amounts of table salt and sodium hydroxide.

Polyalkylene polyamine 2

The base mixture obtained in Example 1 is first under normal pressure, then under reduced Pressure of about loo mbar the remaining water, ethylenediamine as well as, most of the Diethylenetriamine is distilled off and the sodium chloride which separates out is removed by filtration.

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Polyalkylene polyamine 3

In addition to water, ethylenediamine, diethylenediamine, most of the triethylenetetramine is separated off by distillation at a final vacuum of about 10-15 Torr from the base mixture obtained in accordance with Example i, and the inorganics which separate out are also removed by filtration, the
Filtration is facilitated by the addition of kieselguhr and the amine mixture by using activated charcoal

10 can be lightened noticeably.

Reaction products of polyamide amines A and polyalkylene polyamines B with polyfunctional ones Compounds C to the "urea according to the invention group-containing polyamines ".

15 polyamine 1

To 100 g of water, 55 g of polyurea Al) and
38 g of tetraethylene pentamine are placed at 90.degree
35 g of dichloroethane and 3o g of 40% sodium hydroxide solution. The mixture is stirred at this temperature until

a viscosity of 35o mPas is reached. Man
then cools to room temperature, mixed with
so much conc. Hydrochloric acid so that a pH of 5 is established and unconverted diehloroethane is distilled off in vacuo. Sufficient water is added to give a "25% solution, based on the active ingredient content. This solution has a viscosity of 34o mPas at 25 ° C."

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Polyamine 2

Like polyamine 2, but 55 g of polyurea are used Al), 58 g of tetraethylene pentamine, 45 g of dichloroethane and 4o g of 5o% potassium hydroxide solution. The 25% polyamine 2 adjusted to a pH of 5.5 has a viscosity of 32o mPas at 25 ° C.

Polyamine 3 45 g of dichloroethane and 20 g of 50% strength potassium hydroxide solution are added to 80 g of water, 50 g of polyurea A l) and 50 g of polyalkylene B l) at a temperature of 90 ° C. The mixture is stirred at this temperature until a viscosity of. 4oo mPas is reached. It is cooled ah, unreacted dichloroethane is distilled in vacuo ah, a pH value of 5 is set with conc. Hydrochloric acid is added and so much water is added that a 25% solution based on the active ingredient content results. This solution has a viscosity of 25o mPas at 25 ° C.

Polyamine 4 To 80 g of water, 60 g of polyurea A 2) and 60 g of polyalkylenepolyamine B l) are added 40 g at 90 ° C. Dichloroethane and 2o g of 40% sodium hydroxide solution. The mixture is stirred at this temperature until a viscosity of 500 mPas is reached. One cools

25 from, unreacted dichloroethane is distilled off in vacuo, adjusts pH 6 with conc. Hydrochloric acid and add enough water to make a 25% solution based on active ingredient content. These Solution has a viscosity of 25o mPas

25 ⁰ C on.

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Polyamine 5

To 120 g of water, 50 g of polyurea A 3) and 35 g of polyalkylenepolyamine B 3) are added at 75.degree 3o g dichloroethane and 3o g 50% potassium hydroxide solution. The mixture is stirred at this temperature until one Viscosity of 7oo mPas is reached. It is cooled, unreacted dichloroethane is distilled in Vacuum and add so much water that one

25% solution based on active ingredient content results. .jQ This solution has a viscosity of 900 mPas

at 25 ^° C.

Polyamine 6

To 100 g of water, 45 g of polyurea A4) and 2o g

Tetraethylene pentamine is used at 90 ° C. 35 g

Dichloroethane too. The mixture is stirred at this temperature until a viscosity of 50 mPas is reached and then cools down to 70 ° C. At this temperature, condensation takes place up to a viscosity of 4oo mPas, sets 3o g conc. Hydrochloric acid, cools and adjusts to pH 5 with more hydrochloric acid. One distills Excess dichloroethane and sets a 25% solution based on the active ingredient content. The solution has a viscosity of 360 mPas at 25 ° C.

Polyamine 7

To 100 g of water, 50 g of polyurea A l) and 40 g Tetraethylene pentamine is added to 15 g of epichlorohydrin. The condensation is carried out at 40 ° C. up to a viscosity of 250 mPas and adds another 50 g of water. With 'conc. Hydrochloric acid has a pH of 4 and add so much water that a 25 $ solution results. This solution has a viscosity from 22o mPas.

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Polyamine 8

About 2oo g ¥ ater, 12o g Polyurea A 5) and ko g polyalkylenepolyamine B 3), about strength potassium hydroxide solution to at loo ° C 6o g of dichloroethane and 6o g 5o%. The mixture is condensed at 100 ° C. up to a viscosity of 25o mPas. The mixture is cooled, adjusted to pH 5 with concentrated HCl, unreacted dichloroethane is distilled off and so much water is added that a 25% solution based on the active ingredient is added -IO content with a viscosity of 34to mPas at 25 ⁰ C results.

Polyamine 9, loo g water, 50 g polyharastoff A 6) 50 g polyalkylenepolyamine B 2) and 40 g dichloroethane are stirred in a stirred autoclave at a pressure of up to 6 bar and 120 ° C. for 1 hour. After releasing the pressure, it is made up to a 24% solution with water. This solution ι 8oo mPas.

This solution has a viscosity of 25 ° C

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example 1

as

On a laboratory paper machine (Kämmerer type), 7o % identical softwood sulfite pulp and
3o % bleached beech sulphate pulp papers
5 (approx. 8o g / m). Once in the
acidic range, on the other hand worked at neutral pH values:

a) Acid area:

Addition of 3o% china clay as filler, 1% resin glue and

3% aluminum sulfate

to paper pulp. The pH was adjusted to 4.5 with sulfuric acid.

b) Neutral area:

Addition of 3o % calcium carbonate as filler,

1% Aquapel 36o XZ (synthetic

Glue based on stearyl diketene from Hercules Inc.)

to paper pulp; The pH was adjusted to 7.8 to 8 with sodium hydroxide solution.

In front of the headbox of the paper machines, the 1% aqueous solutions were pumped in the 25% polyamines 1 to 7 are metered in. For comparison were also 1% dilutions of the known retention agent polyurea I according to Example 15 of US 3,966,684 or the known one

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Retention agent polyethylene polyamine II (ÜS-PS 3 972 939, example 1) and mixtures of I: II in a ratio of 75: 25%, 5o: 5o% and 25: 75% metered in.

As a measure of the retention effect, the Solid content in the wastewater from the paper machine certainly. The lower this solids content, the more so ■ the retention effect is better.

The following Table 1 illustrates that the polyamines according to the invention both in the acidic as in the neutral area has a very good retention effect and that this is better than that when using mixtures of polyurea and polyethylene polyamine retention aids. The additional amounts each refer to the weight of the air-dry pulp and the 25% solution of the retention aid.

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Table 1

Retention additive
medium amount I. 1 o, l% Il Dry residue
mg / 1 in wastewater II 2 " II a) more acidic
area
pH 4.3 more neutral
area
pH 7.8 without mixture 3 75% I "
25% Ii 643 785 Polyamine mixture 4 " 5o% I "
5o% II 182 181 Il mixture 5 25% ι "
75% II 171 161 M. 6th 195 190 Il 7th 186 I92 Il 8th " 188 195 Il 9 165 172 Il 187 184 Il 185 188 H 213 312 219 197 2o3 286 2o8 271 212 235

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ORIGINAL INSPECTED

- 25 -

Application example 2

As a measure of the dewatering acceleration to be expected on a paper machine in practice the Schopper-Riegler freeness was determined. The stronger the grind due to the added Retention agent is decreased, the better the expected dewatering acceleration.

Another measure of the dewatering acceleration to be expected on a paper machine is the so-called drainage time. This is determined by using the Schopper-Riegler freeness tester the time is measured, which is required to set a certain degree of grinding or water volume is required in the flow cup. The shorter this time, the better the achievable Dewatering acceleration.

A mixture of 3o% unglued. Sulphate, 40% clay and 70 % wood pulp were whipped on the high-speed stirrer and the pH was adjusted:

a) Acid area:

Addition of 0.5 % aluminum sulfate, adjustment of pH 5 »2 with sulfuric acid.

b) Neutral area:

Adjustment of pH 7.2 with sodium hydroxide solution.

To 2oo ml of the 1 following paper stock suspension prepared according to a) or b) was added in each case

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the 1% solution was made up to 100 ml with water and with the help of the Schopper-Riegler device the degree of grinding "is determined.

The additional amounts each relate to the weight of the air-dry paper stock and to the 25% solution of polyamines 1 "to 7.

Table 2 below illustrates the good drainage effect of the polyalkylenepolyamines according to the invention both in the acidic and in the neutral range. For comparison, the known ones listed in Application Example 1 were also used Retention agent metered in.

In addition to the degree of grinding, the tables also show the drainage time in see. listed that until reaching 15 of a certain degree of grinding was necessary. This grind should be a little below the grind of the paper pulp lying without the addition of a retention aid.

If, in Table 2, the overall properties of each individual product in an acidic, weakly alkaline environment, with 0.1 and 0.2 % addition, are taken together, the products according to the invention have a better dewatering acceleration than the known ones.

Le A 19 639

030064/0165

Tabel

pH 7.5 Degree of grinding / ° SR? 30% unbleached sulfate
70% wood pulp
40% clay additive
in % 68 example 5o
4o Drainage / secu / b < without 0.1
o, 2 49
48 117 1 oil
0.2 49
47 65.8
63.2 2 0.1
0.2 51
48 68.4
62.2 3 oil
o, 2 5o
48 67.6
64.1 4th 0.1
0.2 51
49 68.9
64.5 5 oil
0.2 49
47 7o, o
63.8 6th 0.1
0.2 49
48 69.5
59.2 7th oil
o, 2 67.5
62.9 8th 67.5
64.6

pH 5.2 + 0.5% alum + H "SO ₄

Degree of grinding / ° SR / drainage

/lake? at 55 ⁰ SR

58

llo, 5

5ο 69.5 ι ι N) 46 5ο, 7 O, CD
to 51 69.4 t cn 47 51.4 cn 49 67.8 co 46 5ο, 7 -j 52 67.5 47 49.3 5ο 67.4 46 51.2 5ο 71.1 45 53, ο 49 68.4 47 51.6 49 7ο, 2 46 49.3

VO CTl

pH 7.5

Example addition in%

Table 2 (continued)

30% unbleached Sulphate 70% wood pulp 40% clay

Degree of grinding / ° SR? Drainage / lake / at 65 ° SR pH 5.2 + 0.5% alum + H "SO

Degree of grinding / ⁰ SR / drainage

/ see / at 55 ⁰ SR

ο, Ι ο, 2

5ο

68, ο 63.8 49 47

69.8 5ο, 1

I.
II

mixture
j

ο, Ι 0.2

ο, Ι ο, 2

53 5ο

51 49

75.2 68, ή

68.9 64.3 51 5ο

53 52

32 51

74.9 55.8

76.9 58.7

• ι

cn cn co

Claims (9)

Patent claims: 1.) Non-crosslinking, water-soluble polyamines, obtained by reacting A) basic polyureas, which are produced by condensation of urea with polyamines containing at least three Contain amino groups, at least one of which is a tertiary amino group, or mixtures of these Polyamines with two primary or two secondary amino groups containing aliphatic, araliphatic, cycloaliphatic or heterocyclic polyamines and optionally with at least three Tx / -aminocarboxylic acids containing carbon atoms or whose lactams have been produced, B) Polyalkylenepolyamines of the general formula CH ₂ -CH- (CH ₂ ) y -JiH | £ H -JiH ~ | £ ⁱⁿ RH or CH- Y · identical or different the number 0 or 1 and x is a number from k to 2500 Le A 19 639 030064/0165 ORIGINAL INSPECTED or mixtures of these polyalkylene polyamines with amines of the same formula in which χ is a number from 1 to 3 and
C) Compounds which are polyfunctional towards amino groups. 2.) Polyamines according to claim 1, characterized / that they have an average molecular weight of over 5000 have. 3.) polyamines according to claim 1, characterized in that that in the implementation of A, B and C practical all functional groups of the polyfunctional compound have reacted. 4.) polyamines according to claims 1-3, characterized in that that as basic ureas A the condensation -I5 products are used that are available by condensation of a) 1 mol of urea with b) 0.7 to 1.5 mol of the amine or the amine mixture, in particular 0.8 to 1.2 moles. 5.) Polyamines according to Claims 1 - 4, characterized in that that the basic ureas A and polyalkylenepolyamines B in weight ratios of 1 to 10:10 to, in particular 1 to 2.5: 2.5 to 1, can be used. Le A 19 639 030064/0165 6.) Polyamines according to claims 1-5, characterized in that that the reaction of the reactants A, B and C in an aqueous medium at temperatures 0 to 140 ° C, a total concentration of 10 - 60 and pH values above 6 can be carried out. 7.) Polyamines according to Claims 1-6, characterized in that that the reaction is carried out at pressures from 0 to bar, in particular from 3 to 8 bar. 8.) Process for the preparation of water-soluble amines, characterized in that the reactants A, B and C according to claim 1 are reacted with one another. 9.) Use of the water-soluble polyamines according to claim 1 as an aid to increase retention of fibers, fillers and pigments and as dewatering accelerators in paper manufacture and for processing paper machine waste water by filtration, sedimentation and Flotation. 1O.) Aids to increase the reaction of fibers, Fillers and pigments and dehydration accelerators in paper production and for processing paper machine waste water Filtration, sedimentation and flotation containing water-soluble polyamines as the active ingredient according to claim 1. Le A 19 639 030064/0165